WO2016023400A1 - 正极复合材料及锂离子电池 - Google Patents

正极复合材料及锂离子电池 Download PDF

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WO2016023400A1
WO2016023400A1 PCT/CN2015/081514 CN2015081514W WO2016023400A1 WO 2016023400 A1 WO2016023400 A1 WO 2016023400A1 CN 2015081514 W CN2015081514 W CN 2015081514W WO 2016023400 A1 WO2016023400 A1 WO 2016023400A1
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positive electrode
ion battery
lithium ion
monomer
electrode composite
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PCT/CN2015/081514
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English (en)
French (fr)
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何向明
钱冠男
尚玉明
王莉
杨聚平
李建军
赵鹏
高剑
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江苏华东锂电技术研究院有限公司
清华大学
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Publication of WO2016023400A1 publication Critical patent/WO2016023400A1/zh
Priority to US15/428,383 priority Critical patent/US20170155128A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a positive electrode composite material and a lithium ion battery using the same.
  • lithium-ion batteries have the advantages of high energy density, long cycle life, no memory effect and low environmental pollution.
  • lithium battery explosions and injuries in mobile phones and notebook computers have occurred frequently, and the safety of lithium-ion batteries has attracted widespread attention.
  • Lithium-ion batteries emit a large amount of heat in the case of excessive charge and discharge, short circuit, and long-time operation of large currents. Thermal runaway may cause battery burning or explosion, and applications such as electric vehicles have more stringent safety requirements for batteries. . Therefore, the safety research of lithium ion batteries is of great significance.
  • a lithium ion battery positive electrode composite material comprising a positive electrode active material and a maleimide monomer compounded with the positive electrode active material, the positive electrode active material being a lithium-transition metal oxide, the maleimide single
  • the body includes at least one of a maleimide monomer, a bismaleimide monomer, a polymaleimide monomer, and a maleimide derivative monomer.
  • a lithium ion battery comprises a positive electrode, a negative electrode, a separator and an electrolyte solution, and the positive electrode comprises the above-mentioned lithium ion battery positive electrode composite material.
  • the invention adds the maleimide monomer to the positive electrode of the lithium ion battery, and can improve the electrode stability and thermal stability of the lithium ion battery without affecting the charge and discharge cycle performance of the lithium ion battery.
  • Embodiment 1 is a graph showing charge and discharge cycle performance of a lithium ion battery according to Embodiment 1 of the present invention.
  • FIG. 2 is a graph showing changes in voltage and temperature of a battery during overcharge of a lithium ion battery according to Embodiment 1 of the present invention.
  • FIG. 3 is a graph showing voltage versus temperature versus time for overcharge of a lithium ion battery of Comparative Example 1.
  • the lithium ion battery cathode composite material and the lithium ion battery using the cathode composite material provided by the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
  • Embodiments of the present invention provide a positive electrode composite material for a lithium ion battery, comprising a positive electrode active material and a maleimide monomer compounded with the positive electrode active material.
  • the positive electrode active material is a lithium-transition metal oxide.
  • the maleimide monomer may be uniformly mixed with the positive electrode active material or coated on the surface of the positive electrode active material.
  • the mass percentage of the maleimide monomer in the positive electrode composite may be from 0.01% to 10%, preferably from 1% to 5%, more preferably 3%.
  • the maleimide monomer includes at least one of a maleimide monomer, a bismaleimide monomer, a polymaleimide monomer, and a maleimide derivative monomer.
  • the molecular formula of the maleimide monomer can be represented by the formula (1).
  • R 1 is -R, -RNH 2 R, -C(O)CH 3 , -CH 2 OCH 3 , -CH 2 S(O)CH 3 , -C 6 H 5 , -C 6 H 4 C 6 H 5 , -CH 2 (C 6 H 4 )CH 3 , cycloaliphatic, silane-substituted aromatic or halogenated aromatic.
  • R is an alkyl group of 1 to 6 carbons.
  • the maleimide monomer may be selected from the group consisting of N-phenylmaleimide, N-(o-methylphenyl)-maleimide, N-(m-methylphenyl)- Maleimide, N-(p-methylphenyl)-maleimide, N-cyclohexanemaleimide, maleimide, maleimidophenol, Malay Imidazobenzocyclobutene, xylyl maleimide, N-methylmaleimide, vinyl maleimide, thiomaleimide, maleimide One or more of a ketone, a methylene maleimide, a maleimide methyl ether, a maleimido ethylene glycol, and a 4-maleimide phenyl sulfone.
  • the molecular formula of the bismaleimide monomer can be represented by the formula (2).
  • R 2 is -R-, -RNH 2 R-, -C(O)CH 2 -, -CH 2 OCH 2 -, -C(O)-, -O-, -OO-, -S-, -SS -,-S(O)-,-CH 2 S(O)CH 2 -,-(O)S(O)-, -C 6 H 4 -, -CH 2 (C 6 H 4 )CH 2 -, -CH 2 (C 6 H 5 )(O)-, phenyl (-C 6 H 4 -), biphenyl (-C 6 H 4 C 6 H 4 -), substituted phenyl or substituted a biphenyl group, a silane-substituted aromatic or halogenated aromatic, or -(C 6 H 4 )-R 5 -(C 6 H 4 )- , wherein R 5 is -CH 2 -, -C ( O)-, -C(CH 3 )
  • the bismaleimide monomer may be selected from the group consisting of N,N'-bismaleimide-4,4'-diphenylmethane, 1,1'-(methylenebis-4 , 1-phenylene) bismaleimide, N,N'-(1,1'-diphenyl-4,4'-dimethylene) bismaleimide, N,N' -(4-methyl-1,3-phenylene) bismaleimide, 1,1'-(3,3'-dimethyl-1,1'-diphenyl-4,4' -Dimethylene) bismaleimide, N,N'-vinyl bismaleimide, N,N'-butenyl bismaleimide, N,N'-(1, 2-phenylene) bismaleimide, N,N'-(1,3-phenylene) bismaleimide, N,N'-bismaleimide sulfur, N,N '-Bismaleimide disulfide, N,N'-bismaleimide, N,N'-methylene
  • the maleimide derivative monomer can be obtained from the maleimide group in the above maleimide monomer, bismaleimide monomer or polymaleimide monomer
  • the H atom is substituted with a halogen atom.
  • the positive electrode active material may specifically be at least one of a lithium-transition metal oxide having a layer structure, a lithium-transition metal oxide having a spinel structure, and a lithium-transition metal oxide having an olivine structure.
  • Li x Ni 1-y L y O 2 , Li x Co 1-y L y O 2 , Li x Mn 1-y L y O 2 , Li x Fe 1-y L y PO 4 , Li x Ni 0.5+za Mn 1.5-zb L a R b O 4 , Li x Ni c Co d Mn e L f O 2 , or Li x Mn 2-i L i O 4 represents, where 0.1 ⁇ x ⁇ 1.1, 0 ⁇ y ⁇ 1 ( Preferably, it is 0.1 ⁇ y ⁇ 0.5), 0 ⁇ z ⁇ 1.5 (preferably 0 ⁇ z ⁇ 0.1), 0 ⁇ az ⁇ 0.5, 0 ⁇ b + z
  • the positive electrode active material may be olivine-type lithium iron phosphate, layered structure lithium cobaltate, layered structure lithium manganate, layered lithium nickelate, spinel-type lithium manganate, lithium nickel manganese oxide. And lithium nickel cobalt manganese oxide.
  • the positive electrode composite material may further include a conductive agent and/or a binder.
  • the conductive agent may be one or more of a carbon material such as carbon black, a conductive polymer, acetylene black, carbon fiber, carbon nanotubes, and graphite.
  • the binder may be one of polyvinylidene fluoride (PVDF), poly(vinylidene fluoride), polytetrafluoroethylene (PTFE), fluorine rubber, ethylene propylene diene monomer, and styrene butadiene rubber (SBR). Or a variety.
  • the components in the positive electrode composite material may be uniformly dispersed in an organic solvent, sufficiently stirred to form a uniform mixed slurry, coated on the surface of the positive electrode current collector, and the organic solvent in the slurry is evaporated to form a positive electrode.
  • a layer of a maleimide monomer may be coated on the surface of the positive electrode active material to form a core-shell structure, and then mixed with other components, a slurry coating and a drying step to form a positive electrode.
  • the maleimide monomer may be melted or dissolved in an organic solvent to form a solution, and the positive electrode active material may be put into the liquid containing the maleimide monomer, stirred, removed, filtered, and baked. Dry to form a coating layer of a maleimide monomer on the surface of the positive electrode active material particles.
  • the maleimide monomer is uniformly mixed with the positive electrode active material, and is applied as a component of the positive electrode composite material on the surface of the positive electrode current collector, so that the maleic imide is provided both outside and inside the positive electrode composite material layer.
  • the monomer especially when the maleimide monomer is coated on the surface of the positive electrode active material particle, can effectively protect the positive electrode active material under an overvoltage, avoid thermal runaway, and improve thermal stability.
  • the embodiment of the invention further provides a lithium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte solution.
  • the positive electrode and the negative electrode are spaced apart from each other by the separator.
  • the positive electrode may further include a positive electrode current collector and the positive electrode composite material disposed on the surface of the positive electrode current collector.
  • the negative electrode may further include a negative current collector and a negative electrode material disposed on a surface of the negative current collector. The negative electrode material is opposed to the above positive electrode composite material and disposed at intervals by the separator.
  • the negative electrode material may include a negative electrode active material, and may further include a conductive agent and a binder.
  • the negative electrode active material may be at least one of lithium titanate, graphite, phase carbon microspheres (MCMB), acetylene black, microbead carbon, carbon fibers, carbon nanotubes, and pyrolysis carbon.
  • the conductive agent may be one or more of a carbon material such as carbon black, a conductive polymer, acetylene black, carbon fiber, carbon nanotubes, and graphite.
  • the binder may be one of polyvinylidene fluoride (PVDF), poly(vinylidene fluoride), polytetrafluoroethylene (PTFE), fluorine rubber, ethylene propylene diene monomer, and styrene butadiene rubber (SBR). Or a variety.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • the separator may be a polyolefin porous film, a modified polypropylene felt, a polyethylene felt, a glass fiber felt, an ultrafine glass fiber paper vinylon felt or a nylon felt and a wettable polyolefin microporous film welded or bonded. Composite film.
  • the electrolyte solution includes a lithium salt and a non-aqueous solvent.
  • the nonaqueous solvent may include one or more of a cyclic carbonate, a chain carbonate, a cyclic ether, a chain ether, a nitrile, and an amide, such as ethylene carbonate (EC), diethyl carbonate.
  • EC ethylene carbonate
  • Ester (DEC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), butylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, dipropyl carbonate, N-methylpyrrolidone (NMP), N-methylformamide, N-methylacetamide, dimethylformamide, diethylformamide, diethyl ether, acetonitrile, propionitrile, anisole, succinonitrile , adiponitrile, glutaronitrile, dimethyl sulfoxide, dimethyl sulfite, vinylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, fluoroethylene carbonate, chlorocarbonate Ester, acid anhydride, sulfolane, methoxymethyl sulfone, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, methyl acetate
  • the lithium salt may include lithium chloride (LiCl), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium methanesulfonate (LiCH 3 SO 3 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) Lithium hexafluoroarsenate (LiAsF 6 ), lithium hexafluoroantimonate (LiSbF 6 ), lithium perchlorate (LiClO 4 ), Li[BF 2 (C 2 O 4 )], Li[PF 2 (C 2 O) 4 ) one or more of 2 ], Li[N(CF 3 SO 2 ) 2 ], Li[C(CF 3 SO 2 ) 3 ], and lithium bis(oxalate)borate (LiBOB).
  • LiCl lithium chloride
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • N-phenylmaleimide 80% LiNi 1/3 Co 1/3 Mn 1/3 O 2 , 3% N-phenyl maleimide, 7% PVDF and 10% conductive graphite by mass percentage, using NMP
  • the slurry was applied onto an aluminum foil and dried under vacuum at 120 ° C for 12 hours to prepare a positive electrode.
  • the structural formula of N-phenylmaleimide is represented by the formula (3).
  • LiNi by mass percentage 1/3 Co 1/3 Mn 1/3 O 2 7% of PVDF and 10% of conductive graphite were mixed, dispersed with NMP, and the slurry was coated on an aluminum foil and vacuum-dried at 120 ° C for 12 hours to prepare a positive electrode material.
  • the constant current was charged at a current of 0.2 C between 2.8 and 4.3 V, and the current was discharged at a constant current of 0.2 C, and the cycle was performed 30 times.
  • the half-cells of Examples 1 to 4 and the comparative examples were subjected to charge and discharge cycle performance tests. Referring to FIG. 1 and Table 1, it can be seen that the difference in charge-discharge cycle performance between the maleimide monomer and the half-cell without the maleimide monomer is not significant, so it can be judged that When the normal voltage range is charged and discharged, the addition of the maleimide monomer does not adversely affect the charge and discharge cycle performance of the lithium ion battery.
  • Example 1 and Comparative Example 1 were subjected to an overcharge test.
  • the charging rate is 1C
  • the cut-off voltage is 10V
  • the maximum temperature of the battery of Embodiment 1 is only about 97 °C
  • the battery does not show obvious deformation during the overcharging process; while the battery of Comparative Example 1 has been ignited and burned when the battery is overcharged to 8V, the temperature is as high as 500 ° C.
  • the overcharge test of the other examples is shown in Table 2.
  • the lithium ion battery to which the maleimide monomer was added to the positive electrode had better overcharge resistance.
  • the maleimide monomer is not polymerized with other substances to form a polymer, but is directly used as an additive. Adding maleimide monomer to the positive electrode of lithium ion battery can improve the electrode stability and thermal stability of lithium ion battery without affecting the charge and discharge cycle performance of lithium ion battery. The role.

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Abstract

本发明涉及一种锂离子电池正极复合材料，包括正极活性物质及与该正极活性物质复合的马来酰亚胺类单体，该正极活性物质为锂-过渡金属氧化物，该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种。本发明还涉及一种锂离子电池。

Description

正极复合材料及锂离子电池 技术领域
本发明涉及一种正极复合材料及应用该正极复合材料的锂离子电池。
背景技术
随着便携式电子产品的快速发展和普遍化，锂离子电池的市场需求与日俱增。与传统二次电池相比，锂离子电池具有能量密度高、循环寿命长、无记忆效应和环境污染小等优点。然而，近年来用于手机、笔记本电脑中的锂电池爆炸伤人事件屡屡发生，锂离子电池的安全问题已引起人们的广泛关注。锂离子电池在过度充放电、短路以及大电流长时间工作的情形下会释放出大量的热，可能发生热失控引起电池燃烧或爆炸，而电动汽车等应用领域对电池有更加严苛的安全要求。因此，锂离子电池的安全性研究具有重要意义。
发明内容
有鉴于此，确有必要提供一种能够提高锂离子电池安全性能的锂离子电池正极复合材料及其制备方法以及应用该正极复合材料的锂离子电池。
一种锂离子电池正极复合材料，包括正极活性物质及与该正极活性物质复合的马来酰亚胺类单体，该正极活性物质为锂-过渡金属氧化物，该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种。
一种锂离子电池，包括正极、负极、隔膜及电解质溶液，该正极包括上述锂离子电池正极复合材料。
本发明将马来酰亚胺类单体加入到锂离子电池正极中，在不影响锂离子电池充放电循环性能的前提下，能够提高锂离子电池的电极稳定性及热稳定性，起到过充保护的作用。
 附图说明
图1为本发明实施例1的锂离子电池的充放电循环性能曲线。
图2为本发明实施例1的锂离子电池的过充电时电池的电压及温度随时间变化曲线。
图3为比较例1的锂离子电池的过充电时电池的电压及温度随时间变化曲线。
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面将结合附图及具体实施例对本发明提供的锂离子电池正极复合材料及应用该正极复合材料的锂离子电池作进一步的详细说明。
本发明实施方式提供一种锂离子电池正极复合材料，包括正极活性物质及与该正极活性物质复合的马来酰亚胺类单体。该正极活性物质为锂-过渡金属氧化物。该马来酰亚胺类单体可以与该正极活性物质均匀混合，或者包覆于正极活性物质表面。该马来酰亚胺类单体在该正极复合材料中的质量百分含量可以为0.01%~10%，优选为1%~5%，更优选为3%。
该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种。
该马来酰亚胺单体的分子通式可以由式(1)表示。
Figure WO062-appb-I000001
(1)
R1为-R, -RNH2R, -C(O)CH3，-CH2OCH3, -CH2S(O)CH3, -C6H5, -C6H4C6H5，-CH2(C6H4)CH3，环脂族，硅烷取代的芳香族或卤代的芳香族。R为1-6个碳的烷基。
具体地，该马来酰亚胺单体可以选自N-苯基马来酰亚胺、N-(邻甲基苯基)-马来酰亚胺、N-(间甲基苯基)-马来酰亚胺、N-(对甲基苯基)-马来酰亚胺、N-环己烷基马来酰亚胺、马来酰亚胺、马来酰亚胺基酚、马来酰亚胺基苯并环丁烯、二甲苯基马来酰亚胺、N-甲基马来酰亚胺、乙烯基马来酰亚胺、硫代马来酰亚胺、马来酰亚胺酮、亚甲基马来酰亚胺、马来酰亚胺甲醚、马来酰亚胺基乙二醇及4-马来酰亚胺苯砜中的一种或多种。
该双马来酰亚胺单体的分子通式可以由式(2)表示。
Figure WO062-appb-I000002
(2)
R2为-R-，-RNH2R-，-C(O)CH2-，-CH2OCH2-，-C(O)-，-O-，-O-O-，-S-，-S-S-，-S(O)-，-CH2S(O)CH2-，-(O)S(O)-，-C6H4-，-CH2(C6H4)CH2-，-CH2(C6H5)(O)-，伸苯基（-C6H4-），伸联苯基（-C6H4C6H4-），取代的伸苯基或取代的伸联苯基，硅烷取代的芳香族或卤代的芳香族，或-(C6H4)-R5-(C6H4)- ，其中R5为-CH2-，-C(O)-，-C(CH3)2-，-O-，-O-O-，-S-，-S-S-，-S(O)-，-(O)S(O)-。其中R为1-6个碳的烷基。
具体地，该双马来酰亚胺单体可以选自N,N’-双马来酰亚胺-4,4’-二苯基代甲烷、1,1’-(亚甲基双-4,1-亚苯基)双马来酰亚胺、N,N’-(1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺、N,N’-(4-甲基-1,3-亚苯基)双马来酰亚胺、1,1’-(3,3’-二甲基-1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺、N,N’-乙烯基双马来酰亚胺、N,N’-丁烯基双马来酰亚胺、N,N’-(1,2-亚苯基)双马来酰亚胺、N,N’-(1,3-亚苯基)双马来酰亚胺、N,N’-双马来酰亚胺硫、N,N’-双马来酰亚胺二硫、N,N’-双马来酰亚胺亚胺酮、N,N’-亚甲基双马来酰亚胺、双马来酰亚胺甲醚、1,2-双马来酰亚胺基-1,2-乙二醇、N,N’-4,4’-二苯醚-双马来酰亚胺及4,4’-双马来酰亚胺-二苯砜中的一种或多种。
该马来酰亚胺类衍生物单体可通过将上述马来酰亚胺单体、双马来酰亚胺单体或多马来酰亚胺单体中马来酰亚胺基团中的H原子以卤素原子取代。
该正极活性物质具体可以为层状结构的锂-过渡金属氧化物，尖晶石型结构的锂-过渡金属氧化物以及橄榄石型结构的锂-过渡金属氧化物中的至少一种，由化学式LixNi1-yLyO2，LixCo1-yLyO2，LixMn1-yLyO2，LixFe1-yLyPO4，LixNi0.5+z-aMn1.5-z-bLaRbO4，LixNicCodMneLfO2，或LixMn2-iLiO4表示，其中0.1≤x≤1.1, 0≤y<1 （优选为0.1<y<0.5）, 0≤z<1.5 （优选为0≤z<0.1）, 0≤a-z<0.5, 0≤b+z<1.5, 0<c<1, 0<d<1, 0<e<1, 0≤f≤0.2, c+d+e+f=1, 且 0≤i<2，L与R选自碱金属元素、碱土金属元素、第13族元素、第14族元素、过渡族元素及稀土元素中的一种或多种，优选为Mn、Cr、Co、Ni、V、Ti、Al、Ga及Mg中的至少一种。更为优选地，该正极活性物质可以为橄榄石型磷酸铁锂、层状结构钴酸锂、层状结构锰酸锂、层状镍酸锂、尖晶石型锰酸锂、锂镍锰氧化物及锂镍钴锰氧化物。
该正极复合材料可进一步包括导电剂和/或粘结剂。该导电剂可以为碳素材料，如碳黑、导电聚合物、乙炔黑、碳纤维、碳纳米管及石墨中的一种或多种。该粘结剂可以是聚偏氟乙烯(PVDF)、聚偏（二）氟乙烯、聚四氟乙烯(PTFE)、氟类橡胶、三元乙丙橡胶及丁苯橡胶(SBR)中的一种或多种。
该正极复合材料中的各组分可以共同分散在有机溶剂中，充分搅拌从而形成均匀混合浆料，涂覆于正极集流体表面，使浆料中的有机溶剂蒸发，从而形成正极。另外，也可以预先在正极活性物质表面包覆一层马来酰亚胺类单体层，形成核-壳结构，再与其它组分进行混合、浆料涂覆和烘干步骤，形成正极。具体地，可以将马来酰亚胺类单体熔融或溶于有机溶剂形成溶液，再将正极活性物质投入该含马来酰亚胺类单体的液体中，搅拌后捞出、过滤并烘干，从而在正极活性物质颗粒表面形成马来酰亚胺类单体的包覆层。
该马来酰亚胺类单体与该正极活性物质均匀混合，作为正极复合材料的组分涂覆在正极集流体表面，使正极复合材料层的外部和内部都具有该马来酰亚胺类单体，尤其是当该马来酰亚胺类单体包覆在正极活性物质颗粒表面时，能够在过电压下有效保护正极活性物质，避免热失控发生，提高热稳定性。
本发明实施例进一步提供一种锂离子电池，包括正极、负极、隔膜及电解质溶液。该正极与负极通过所述隔膜相互间隔。所述正极可进一步包括一正极集流体及设置在该正极集流体表面的所述正极复合材料。所述负极可进一步包括一负极集流体及设置在该负极集流体表面的负极材料。该负极材料与上述正极复合材料相对且通过所述隔膜间隔设置。
该负极材料可包括负极活性物质，并可进一步包括导电剂及粘结剂。该负极活性物质可以为钛酸锂、石墨、相碳微球(MCMB)、乙炔黑、微珠碳、碳纤维、碳纳米管及裂解碳中的至少一种。该导电剂可以为碳素材料，如碳黑、导电聚合物、乙炔黑、碳纤维、碳纳米管及石墨中的一种或多种。该粘结剂可以是聚偏氟乙烯(PVDF)、聚偏（二）氟乙烯、聚四氟乙烯(PTFE)、氟类橡胶、三元乙丙橡胶及丁苯橡胶(SBR)中的一种或多种。
所述隔膜可以为聚烯烃多孔膜、改性聚丙烯毡、聚乙烯毡、玻璃纤维毡、超细玻璃纤维纸维尼纶毡或尼龙毡与可湿性聚烯烃微孔膜经焊接或粘接而成的复合膜。
该电解质溶液包括锂盐及非水溶剂。该非水溶剂可包括环状碳酸酯、链状碳酸酯、环状醚类、链状醚类、腈类及酰胺类中的一种或多种，如碳酸乙烯酯（EC）、碳酸二乙酯（DEC）、碳酸丙烯酯（PC）、碳酸二甲酯（DMC）、碳酸甲乙酯（EMC）、碳酸丁烯酯、γ-丁内酯、γ-戊内酯、碳酸二丙酯、N-甲基吡咯烷酮(NMP)、N-甲基甲酰胺、N-甲基乙酰胺、二甲基甲酰胺、二乙基甲酰胺、二乙醚、乙腈、丙腈、苯甲醚、丁二腈、己二腈、戊二腈、二甲亚砜、亚硫酸二甲酯、碳酸亚乙烯酯、碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯、氟代碳酸乙烯酯、氯代碳酸丙烯酯、酸酐、环丁砜、甲氧基甲基砜、四氢呋喃、2-甲基四氢呋喃、环氧丙烷、乙酸甲酯、乙酸乙酯、乙酸丙酯、丁酸甲酯、丙酸乙酯、丙酸甲酯、二甲基甲酰胺、1,3-二氧戊烷、1,2-二乙氧基乙烷、1,2-二甲氧基乙烷、或1,2-二丁氧基中的一种或几种的组合。
该锂盐可包括氯化锂（LiCl）、六氟磷酸锂（LiPF6）、四氟硼酸锂（LiBF4）、甲磺酸锂（LiCH3SO3）、三氟甲磺酸锂（LiCF3SO3）、六氟砷酸锂（LiAsF6）、六氟锑酸锂（LiSbF6）、高氯酸锂（LiClO4）、Li[BF2(C2O4)]、Li[PF2(C2O4)2]、Li[N(CF3SO2)2]、Li[C(CF3SO2)3]及双草酸硼酸锂（LiBOB）中的一种或多种。
实施例1：
半电池的组装：
按质量百分比，将80%的LiNi1/3Co1/3Mn1/3O2、3%的N-苯基马来酰亚胺、7%的PVDF和10%的导电石墨混合，用NMP分散，将此浆料涂布于铝箔上，于120℃真空干燥12小时，制成正极。以锂片作为对电极，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，组装成2032扣式电池，进行充放电性能测试。N-苯基马来酰亚胺的结构式如式(3)所示。
Figure WO062-appb-I000003
(3)
全电池的组装：
按质量百分比，将94%的石墨负极、3.5%的PVDF和2.5%的导电石墨混合，用NMP分散，将此浆料涂布于铜箔上，于100℃真空干燥，压缩并裁剪制成电池负极。正极与半电池相同，将正负极匹配，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，通过卷绕工艺制成63.5 mm * 51.5 mm * 4.0 mm的软包电池。
实施例2：
半电池的组装：
按质量百分比，将80%的LiNi1/3Co1/3Mn1/3O2、3%的双马来酰亚胺、7%的PVDF和10%的导电石墨混合，用NMP分散，将此浆料涂布于铝箔上，于120℃真空干燥12小时，制成正极材料。以锂片作为对电极，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，组装成2032扣式电池，进行充放电性能测试。双马来酰亚胺结构式如式(4)所示。
Figure WO062-appb-I000004
(4)
全电池的组装：
按质量百分比，将94%的石墨负极、3.5%的PVDF和2.5%的导电石墨混合，用NMP分散，将此浆料涂布于铜箔上，于100℃真空干燥，压缩并裁剪制成电池负极。正极与半电池相同，将正负极匹配，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，通过卷绕工艺制成63.5 mm * 51.5 mm * 4.0 mm的软包电池。
实施例3：
半电池的组装：
按质量百分比，将80%的LiNi1/3Co1/3Mn1/3O2、3%的双马来酰亚胺、7%的PVDF和10%的导电石墨混合，用NMP分散，将此浆料涂布于铝箔上，于120℃真空干燥12小时，制成正极材料。以锂片作为对电极，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，组装成2032扣式电池，进行充放电性能测试。双马来酰亚胺结构式如式(5)所示。
Figure WO062-appb-I000005
(5)
全电池的组装：
按质量百分比，将94%的石墨负极、3.5%的PVDF和2.5%的导电石墨混合，用NMP分散，将此浆料涂布于铜箔上，于100℃真空干燥，压缩并裁剪制成电池负极。正极与半电池相同，将正负极匹配，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，通过卷绕工艺制成63.5 mm * 51.5 mm * 4.0 mm的软包电池。
实施例4：
半电池的组装：
按质量百分比，将80%的LiNi1/3Co1/3Mn1/3O2、3%的N,N’-乙烯基双马来酰亚胺、7%的PVDF和10%的导电石墨混合，用NMP分散，将此浆料涂布于铝箔上，于120℃真空干燥12小时，制成正极材料。以锂片作为对电极，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，组装成2032扣式电池，进行充放电性能测试。
全电池的组装：
按质量百分比，将94%的石墨负极、3.5%的PVDF和2.5%的导电石墨混合，用NMP分散，将此浆料涂布于铜箔上，于100℃真空干燥，压缩并裁剪制成电池负极。正极与半电池相同，将正负极匹配，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，通过卷绕工艺制成63.5 mm * 51.5 mm * 4.0 mm的软包电池。
比较例1：
半电池的组装：
按质量百分比，将83%的LiNi1/3Co1/3Mn1/3O2、7%的PVDF和10%的导电石墨混合，用NMP分散，将此浆料涂布于铝箔上，于120℃真空干燥12小时，制成正极材料。以锂片作为对电极，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，组装成2032扣式电池，进行充放电性能测试。
全电池的组装：
按质量百分比，将94%的LiNi1/3Co1/3Mn1/3O2、3%的PVDF和3%的导电石墨混合，用NMP分散，将此浆料涂布于铝箔上，于120℃真空干燥，压缩并裁剪制成电池正极。
按质量百分比，将94%的石墨负极、3.5%的PVDF和2.5%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铜箔上，于100℃真空干燥，压缩并裁剪制成电池负极。将正负极匹配，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，通过卷绕工艺制成63.5mm*51.5mm*4.0mm的软包电池。
电化学性能测试
在2.8-4.3V电压范围之间以0.2C电流恒流充电，0.2C电流恒流放电，循环30次，将实施例1~4及比较例的半电池进行充放电循环性能测试。请参阅图1及表1，可以看到，加入马来酰亚胺类单体与不加入马来酰亚胺类单体的半电池在充放电循环性能上差别并不显著，因此可以判断在正常电压范围充放电时，该马来酰亚胺类单体的加入不会对该锂离子电池的充放电循环性能带来负面影响。
表1 实施例1~4与比较例1半电池充放电循环性能测试数据表
首次放电比容量(mAh/g) 30次循环放电比容量(mAh/g) 30次循环容量保持率(%)
实施例1 159.8 158.7 99.3
实施例2 165.4 161.2 97.5
实施例3 157.3 151.9 96.6
实施例4 162.5 158.6 97.6
比较例1 163.5 160.3 98
电池过充测试
请参阅图2及图3，将实施例1和比较例1中的电池进行过充测试。充电速率为1C，截止电压为10V，实施例1的电池最高温度仅为97℃左右，过充过程中电池未出现明显形变；而比较例1的电池过充至8V时已经起火燃烧，温度高达500℃。其他实施例的过充电测试见表2，在正极中添加马来酰亚胺类单体的锂离子电池具有更好的耐过充性能。
表2实施例1~4与比较例1全电池耐过充电性能测试数据表
最高温度(℃) 过充现象
实施例1 97℃ 未出现明显形变
实施例2 94℃ 未出现明显形变
实施例3 98℃ 未出现明显形变
实施例4 95℃ 未出现明显形变
比较例1 500℃ 起火燃烧
在该正极复合材料中，该马来酰亚胺类单体并非是与其他物质聚合形成聚合物，而是直接作为添加剂使用。将马来酰亚胺类单体加入到锂离子电池正极中，在不影响锂离子电池充放电循环性能的前提下，能够提高锂离子电池的电极稳定性及热稳定性，起到过充保护的作用。
另外，本领域技术人员还可在本发明精神内做其他变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。

Claims (10)

  1. 一种锂离子电池正极复合材料，包括正极活性物质，其特征在于，进一步包括与该正极活性物质复合的马来酰亚胺类单体，该正极活性物质为锂-过渡金属氧化物，该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种。
  2. 如权利要求1所述的锂离子电池正极复合材料，其特征在于，该马来酰亚胺类单体与该正极活性物质均匀混合。
  3. 如权利要求1所述的锂离子电池正极复合材料，其特征在于，该马来酰亚胺类单体包覆于该正极活性物质表面，形成核-壳结构。
  4. 如权利要求1所述的锂离子电池正极复合材料，其特征在于，该马来酰亚胺单体的分子通式由式(1)表示：
    Figure WO062-appb-I000006
    (1)；
    其中，R1为-R, -RNH2R, -C(O)CH3，-CH2OCH3, -CH2S(O)CH3, -C6H5, -C6H4C6H5，-CH2(C6H4)CH3，环脂族，硅烷取代的芳香族或卤代的芳香族；R为1-6个碳的烷基。
  5. 如权利要求1所述的锂离子电池正极复合材料，其特征在于，该双马来酰亚胺单体的分子通式由式(2)表示：
    Figure WO062-appb-I000007
    (2)；
    其中R2为-R-，-RNH2R-，-C(O)CH2-，-CH2OCH2-，-C(O)-，-O-，-O-O-，-S-，-S-S-，-S(O)-，-CH2S(O)CH2-，-(O)S(O)-，-C6H4-，-CH2(C6H4)CH2-，-CH2(C6H5)(O)-，伸苯基（-C6H4-），伸联苯基（-C6H4C6H4-），取代的伸苯基，取代的伸联苯基，硅烷取代的芳香族，卤代的芳香族或-(C6H4)-R5-(C6H4)-；R5为-CH2-，-C(O)-，-C(CH3)2-，-O-，-O-O-，-S-，-S-S-，-S(O)-，-(O)S(O)-；R为1-6个碳的烷基。
  6. 如权利要求1所述的锂离子电池正极复合材料，其特征在于，该马来酰亚胺类单体在该正极复合材料中的质量百分含量为0.01%~10%。
  7. 如权利要求1所述的锂离子电池正极复合材料，其特征在于，该马来酰亚胺类单体在该正极复合材料中的质量百分含量为1%~5%。
  8. 如权利要求1所述的锂离子电池正极复合材料，其特征在于，该正极活性物质由化学式LixNi1-yLyO2，LixCo1-yLyO2，LixMn1-yLyO2，LixFe1-yLyPO4，LixNi0.5+z-aMn1.5-z-bLaRbO4，LixNicCodMneLfO2，或LixMn2-iLiO4表示，其中0.1≤x≤1.1, 0≤y<1, 0≤z<1.5, 0≤a-z<0.5, 0≤b+z<1.5, 0<c<1, 0<d<1, 0<e<1, 0≤f≤0.2, c+d+e+f=1, 且 0≤i<2，L与R选自碱金属元素、碱土金属元素、第13族元素、第14族元素、过渡族元素及稀土元素中的一种或多种。
  9. 如权利要求8所述的锂离子电池正极复合材料，其特征在于，L与R选自Mn、Cr、Co、Ni、V、Ti、Al、Ga及Mg中的至少一种。
  10. 一种锂离子电池，包括正极、负极、隔膜及电解质溶液，该正极包括如权利要求1~9中任意一项所述的锂离子电池正极复合材料。
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